臺灣博碩士論文加值系統

本專題使用陰離子聚合的方式製備不同分子量之polystyrene-poly(tert-butyl-acrylate)(PS-PtBA)團塊共聚合物。以極低溫之方式，使用配位體之方式，及藉t-BA之高立體障礙來提高t-BA之聚合比例。
在活性聚苯乙烯合成後，加入丙烯酸第三丁酯時之溫度控制至為重要，其影響tBA之轉化率至鉅。以緩慢滴入丙烯酸第三丁酯之方式，使其溫度保持-20℃以下，則tBA的轉化率相對地高許多。
本專題以靜態光散射儀(SLS)分析PS-PtBA,PS,以及PtBA /Dioxane溶液，測重量平均分子量、重心迴轉半徑(Rg)及第二維里係數(A2)，所測結果PS-PtBA,PS,PtBA的重量平均分子量分別為25400,8000,15000g/mol,重心迴轉半徑分別為141,60,144nm；而以DLS所測得PS-PtBA大於CMC的粒徑為524nm,推算出PS-PtBA微胞大約由51個分子所組成。
PS-PtBA或PS混合不同含量比例的SiO2，再經過室溫或烘烤55℃，80℃，105℃兩小時熱處理後的接觸角測試，看出當SiO2含量比例愈高，所測出的接觸角愈大，且PS-PtBA比PS接觸角大。 所測樣品中之接觸角最高為130度；且PS-PtBA所測的接觸角與烘烤溫度成正相關。

The diblock copolymer, polystyrene-b-poly (tert-butylacrylate) (PS-PtBA) with given block chain lengths, was prepared by the anionic polymerization.Using condition, such as very low temperature and ligand, and increasing steric hinderance by means of t-BA can increase conversoin.
The t-BA was added to the living PS anion to prepare the diblock copolymer, where the t-BA was added slowly to keep the temperature always below -20℃. The better temperature control leads to the higher yield in PtBA block. The process of preparing the first block with t-BA is not feasible, since the yield is low.
Dioxane solution of PS-PtBA,PS,and PtBA were determined by static laser scattering(SLS) to analysis molecular weight(MW), Radius of Gyration (Rg),and second osmotic virial coefficient(A2).The Mw of PS-PtBA,PS, PtBA MW are 25400,8000,15000g/mol,respectively.Rg are 141, 60, 144nm, respectively. The hydynamic diameter of PS-PtBA at concentration greater than CMC is 524nm by DLS, thus PS-PtBA micelles are compose by 51 molucules each.
PS-PtBA and PS are mix with different SiO2 content and annealing at 55℃,85℃, 105℃ for 2 hour, respectively.It was found that the higher the SiO2 content ,the higher the contact angle；and the higer the annealing temperature , the higher the contact angle of PS-PtbA

摘要......................................................I
Abstract................................................III
縮寫對照表...............................................V
目錄.....................................................VI
圖目錄...................................................IX
表目錄..................................................XVI
第一章 簡介...............................................1
1.1 以陰離子聚合法合成團塊共聚物..........................1
1.2 團塊共聚物之微相分離與自我組裝........................4
1.3 超疏水構造...........................................12
1.4 目標與目的...........................................14
第二章 實驗..............................................16
2.1 藥品及預處理.........................................16
2.2 反應流程.............................................17
2.3 Polystyrene合成......................................17
2.4 PS-b-PtBA 合成.......................................17
2.5 製備超疏水薄膜.......................................18
2.6 接觸角測量...........................................19
2.7 高分子聚集體水力直徑分析準備.........................19
2.8 折射率差(dn/dc)測試..................................19
2.9 靜態光散射儀(SLS)分析................................20
2.10 固含量,未揮發及轉化率計算...........................21
2.11 GPC分子量分析.......................................21
2.12 FTIR聚合物結構分析..................................21
2.13 SEM表面型態分析.....................................22
2.14 TGA 熱重分析儀......................................22
2.15 表面張力的測定......................................22
第三章 結果與討論........................................30
3.1 PS-PtBA團塊共聚合物的合成............................30
3.2 PS-PtBA團塊共聚合物的結構鑑定........................30
3.3 PS-PtBA團塊共聚物的熱裂解溫度........................31
3.4 PS-PtBA與PS的接觸角測試.............................31
3.5 PS-PtBA/Dioxane溶液之SLS測定.......................32
第四章 結論..............................................55
A. 團塊共聚合物的合成、結構鑑定..........................55
B. 團塊共聚合物的性質探討................................55
參考文獻.................................................57
附錄.....................................................66
A.陰離子聚合反應原理.....................................66
B.微差折射率測定儀,原理及實驗............................70
C. 靜態光散射儀(SLS)原理及實驗...........................71
D. 動態光散射儀(DLS)原理及實驗...........................76
E 實驗相關圖.............................................80

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